Carboxylic acid perfluoroalkyl esters

ABSTRACT

Carboxylic acid perfluoroalkyl esters of the formula WHEREIN Rf is a perfluorinated hydrocarbon radical with 1 to 22 carbon atoms, R is hydrogen or methyl, R1 is chlorine, unsubstituted or substituted phenyl or an alkoxy radical, A1 is a hydrocarbon radical with 2 or 3 carbon atoms derived from monobasic, dibasic or tribasic ethylenically unsaturated carboxylic acids and s is an integer from 1 to 3, and their polymerisation products are provided. The new esters and their polymerisation products are useful for rendering porous or nonporous substrates oil-, water- and dirt-repellent or to provide soil-release- anti soiling finishes.

lijnite I llllubeer-E N Dec. 241-, 1974 CARBOXYLllC ACID PERFLUUROALKYL ESTEIRS Inventors: ll-lelmut Huber-Emden, Basel; Paul Schaier, Riehen, both of Switzerland Assignee: Ciba-Geigy Corporation, Ardsley,

Filed: Oct. 117, 1973 Appl. No.: 407,397

Foreign Application Priority Data Oct. 18, 1972 Switzerland 15243/72 US. Cl 260/486 H, 117/139.5, 117/142, 117/148, 252/56, 26 0/8073, 260/86.1 R, 260/86.1 E, 260/86.3, 260/86.7, 260/485 F, 260/633 Int. Cl. C07c 69/54 Field of Search 1. 260/486 H, 485 F References Cited UNITED STATES PATENTS 7/1969 Katsushima et al 260/486 H 5/1970 Katsushima et a1 260/486 H Primary Examiner-Lorraine A. Weinberger Assistant Examiner--Pau1 Killos Attorney, Agent, or Firmloseph G. Kolodny; Edward McC. Roberts; Prabodh Almaula [57] ABSTRACT Carboxylic acid perfluoroalkyl esters of the formula 7 Claims, No Drawings 1 CARBOXYLHC ACID PERFLUOROALKYL ESTERS The present invention relates to carboxylic acid perfluoroalkyl esters corresponding to the formula oxyalkyl with 2 to l carbon atoms, the radical (CH CH O),,-R, in which R represents alkyl with l to 6 carbon atoms and n is l or 2, or represents an optionally substituted phenyl radical, A, represents a hydrocarbon radical with 2 or 3 carbon atoms that is derived from monobasic, dibasic, or tribasic ethylenically unsaturated carboxylic acids, and s is a whole number from 1 to 3.

The invention relates also to the polymerisation products that can be manufactured from the compounds of the formula (1).

The perfluorinated hydrocarbon radical in formula (I is preferably a straight-chain or branched perfluoroalkyl radical with 4 to 17 carbon atoms and can correspond more or less to the following formulae:

with 1 to 6 carbon atomsand n is l or 2, or a phenyl radical or an alkyl-substituted phenyl radical or an alkyl-substituted phenyl radical with l to 4 carbon atoms in the alkyl chain.

Preferably the carboxylic acid perfluoroalkyl esters correspond to the formula wherein R represents hydrogen or methyl, R represents chlorine or the radical R g-O. in which R, represents alkyl with l to 6 carbon atoms, cyclohexyl, phenyl, or alkoxyalkyl with l to 3 carbon atoms in the alkoxy moiety, A, represents an ethylenically unsaturated hydrocarimn radical that is derived from acrylic, methacrylic, crotonic, vinylacetic, fumaric, maleic, citraconic, mesaconic, aconitic, or methylenemalonic acid, n is awhole number from 4 to l4, and .r is a whole number from 1 to 3.

Compounds of particular interest are those of the forand especially wherein R, represents hydrogen or the methyl radical and R, R R3, n, and n, have the indicated meanings.

The carboxylic acid perfluoroalkyl esters are manufactured by reacting perfluoroalcohols of the formula wherein R; represents a perfluorinated hydrocarbon radical with l to 22 carbons. R represents hydrogen or methyl. R, represents chlorine or the radical R,-O-, in which R, represents alkyl with l to 12 carbon atoms, cycloalkyl with 5 or 6-ring atoms, alkoxyalkyl with 2 to 10 carbon atoms, the radical -(CH CH O)"-R. in which R represents alkyl with l to 6 carbon atoms and n is l or 2, or represents an optionally substituted phe nyl radical, with derivatives of carboxylic acids of the formula A,(COOH), s. wherein A, represents an ethylenically unsaturated radical with 2 or 3 carbon atoms and s is a whole number from I to 3. The perfluoroalcohols of the formula (7) can be obtained e.g. by hydrolysis according to the following reaction:

Perfluoroalcohols containing straight-chain or branched perfluoroalkyl radicals with 4 to 17 carbon atoms are preferably used for this esterification. If appropriate, it is also possible to use mixtures of perfluoroalcohols with perfluoroalkyl chains of different length. These mixtures are formed when the starting materials for the manufacture of the perfluoroalcohols are manufactured by telomerisation processes.

Particularly suitable perfluoroalcohols for the present esterification are those that correspond to the formula wherein R represents hydrogen or methyl, R represents chlorine or the radical R -O-, in which R represents alkyl with l to 6 carbon atoms, cyclohexyl, phenyl, or alkoxyalkyl with l to 3 carbon atoms in the alkoxy moiety, and n is a whole number from 4 to 14.

Particularly suitable are also the perfluoroalcohols of the formula and ( CmHmHCH-OII wherein R represents hydrogen or methyl, R represents chlorine or the radical R;,-O-, in which R' represents alkyl with l to 6 carbon atoms, cyclohexyl, phenyl, or methoxyethyl, and n is a whole number from 6 to 12.

The acid derivatives used in the esterification reaction are derived from unsaturated acids of the formula A (COOH) 2; wherein A represents an ethylenically unsaturated hydrocarbon radical that is derived from acrylic, methacrylic, crotonic, vinylacetic, fumaric, maleic, citraconic, mesaconic, itaconic, aconitic, or methylenemalonic acid, and s is a whole number from 1 to 3. Acrylic acid and methacrylic acid esters of alcohols of the formulae (9) and (10) are particularly suitable compounds. But mention may also be made of fumarates, itaconates, and methylenemalonates.

The perfluoroalcohols are esterified by using preferably acid halides, such as acid chlorides and acid esters, e.g alkyl esters. lf appropriate, the esterification is carried out in the presence ofinorganic or organic, preferably nitrogen-containing, bases. Tertiary amines. e.g. trimethylaminem triethylamine, tributylamine, pyridine, and dimethyl aniline, are particularly suitable.

In general, the reaction of the acid chlorides with the perfluorinated alcohol is preferred since the former are readily accessible and the esterification proceeds rapidly and at low temperatures. The non-existent maleyl chloride and chloromaleyl chloride are of course the exceptions.

In general a two-step synthesis is necessary when using methylenemalonic esters. Using one of the esterification methods described hereinbefore, the malonic lymerised with esters are first manufactured and from these are obtained the methylenemalonic esters, for example by condensing the malonic ester with formaldehyde (cf. E. Haworth and W. H. Perkin, J. Chem. Soc. 73, 339-345 (1898).

On account of their vinyl group, the carboxylic acid perfluoroalkyl esters can be homopolymerised or copoother ethylenically unsaturated copolymerisable compounds.

Homopolymers therefore contain recurring units of the formula wherein R, represents a perfluorinated hydrocarbon radical with l to 22 carbon atoms, R represents hydrogen or methyl, R represents chlorine or the radical R,- 0-, in which R represents alkyl with l to 12 carbon atoms, cycloalkyl with 5 or 6 ring carbon atoms, alkoxyalkyl with 2 to 10 carbon atoms, the radical (CH CH O)-R, in which R represents alkyl with l to 6 carbon atoms and n is l or 2, or represents an optionally substituted phenyl radical, A, represents a hydrocarbon radical with 2 or 3 carbon atoms, and s is a whole number from 1 to 3.

The number of recurring units can be about 10 to 400, which corresponds to a gram-molecular weight wherein R represents hydrogen or methyl, R represents chlorine or the radical R' -O-, in which R' represents alkyl with l to 6 carbon atoms, cyclohexyl, phenyl, or alkoxyalkyl with l to 3 carbon atoms in the alkoxy moiety, A represents a hydrocarbon radical with 2 or 3 carbon atoms, 12 is a whole number from 4 to 14, and s is a whole number from 1 to 3.

In addition to the indicated units for the homopolymers, the copolymers contain recurring units of other ethylenically unsaturated copolymerisable compounds.

The polymerisation of the monomeric perfluoroalkyl monocarboxylic acid esters can take place in solution or in emulsion and in the presence of catalysts that generate free radicals with themselves, with another perfluoroalkyl monocarboxylic acid ester, or with other compounds that can be polymerised to linear polymers.

Examples of suitable compounds for the copolymerisation with the perfluoroalkyl monocarboxylic acid esters are:

a. vinyl esters of organic carboxylic acids, e.g. vinyl acetate, vinyl formiate, vinyl butyrate, vinyl benzoate,

b. vinyl alkyl ketones and vinyl alkyl ethers, such as vinyl methyl ketone and vinyl butyl ether,

c. vinyl halides, such as vinyl chloride, vinyl fluoride, vinylidene chloirde,

d. vinylpyrrolidone.

e. vinyl aryl compounds, e.g. styrene and substituted styrenes,

f. derivatives ofthe acrylic acid series, e.g. acrylic nitrile or acrylic amide preferably derivatives substituted at the amide nitrogen, e.g. N-methylolacrylamide, N- methylolacrylic amide alkyl ether, N,N-dihydroxyethylacrylic amide, N-tert.butyl-acrylic amide and hexametholylmelamine triacrylic amide, and the corresponding quaternised compounds,

g. esters of the acrylic acid series, e.g. esters of acrylic acid, methacrylic acid, a-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, and monoor dialcohols containing from 1 to 18 carbon atoms, or phenols, e.g. ethyl acrylate, glycidyl acrylate, butyacrylate, acrylic acid monoglycol ester, dodecylacrylate, or N- dialkylaminoethylmethacrylate and the corre-' sponding quaternised compound, and

h. polymerisable olefins, sughas isobutylene, butadiene or 2-chlorobutadiene.

Preferably there are used esters, amides or methylol amides of acrylic or methacrylic acid, such as ethyl acrylate, butyl acrylate, glycidal acrylate, glycolmonoacrylate, also calcium acryla'te, acrylic amide, methacrylate, methacrylic amide, N-methyololacrylic amide, N-methylolacrylic amide methyl ether, N- tert.butylacrylic amide; vinyl esters of organic carboxylic acids, such as vinyl. acetate; styrene, vinyl halides, such as vinyl-chloride or vinylidene chloride; or polymerisable olefins, such as isobutylene, or vinyl PY 9 d n;

The copolymers obtained with the use of these comonomers are particularly suitable as oil-repellents and also for the soil-release finishing.

The polymers are composed as a rule of to 100, preferably of 40 to 98, percent by weight of a carboxylic acid perfluoroalkyl ester and of 95 to 0, preferably 60 to 2. percent by weight of another compound. Particular industrial importance attaches to those bi-, terand quaterpolymers that in addition to 40 to 98 percent by weight of the monomer carboxylic acid perfluoroalkyl ester, based on the weight of the monomer, contain a reactive monomer, such as N-methylolacrylic amide, an acrylic ester, such as decylacrylate, and optionally a vinyl ester, such as vinyl acetate.

The manufacture of the polymers by homopolymerisation or copolymerisation of perfluoroalkyl monocarboxylic acid esters with one or more other copolymerisable ethylenically unsaturated monomers is carried out by conventional methods, for example by block polymerisation, bead polymerisation, in aqueous emulsion, or preferably by solvent polymerisation in a solvent suitable for this purpose, e.g. acetone, benzene, sym. dichloroethane, ethyl acetate, or trifluoromethylben Zene.

The polymerisation is effected advantageously with the application of heat, preferably to the boiling temperature of the solvent and accompanied by the addition of catalysts that form peroxidic or other free radicals and are soluble in the reaction medium, e.g. ben zoyl peroxide, lauroyl peroxide, a,a-azoisobutyrodinitrile or potassium peroxide disulphate or redox systerns. e.g. potassium peroxide disulphate/sodium bisulence of substrates. For example, it can be carried out' on glass fibre fabrics or textile material. In this case the respective substrate is advantageously impregnated with solutions or emulsions of the monomers and subsequently the polymerisation is effected by addition of a polymerisation catalyst by heating the material.

The preferred polymerisation processes are emulsion polymerisation in an aqueous medium and solvent polymerisation.

The polymerisation is preferably carried out with a reaction time that is so adjusted that a virtually quantitative conversion of the monomer into the polymer is attained. The maximum reaction time depends on the catalyst used and the polymerisation temperature and also on other conditions, but it is generally in the range from 0.5 to 24 hours.

The polymerisation temperature depends in turn on the chosen catalyst. In the case of emulsion polymerisation in aqueous medium it is in general in the range from 20 to C. Whereever possible, the polymerisation is carried out at atmospheric pressure.

In the emulsion polymerisation, the monomer(s) to be polymerised is (are) polymerised jointly in an aqueous solution of an emulsifier under nitrogen to a given monomer concentration of about 5 to about 50%. Normally the temperature is raised to 40 to 70c in order to effect the polymerisation in the presence if an added catalyst. The concentration of the polymerisation catalyst is generally between 0.1 and 2%, based on the weight of the monomers.

Suitable emulsifiers are cationic, anionic, or nonionic surfactants. The hydrophobic constituent of the emulsifier can be a hydrocarbon or fluorinated hydrocarbon.

Suitable cationic emulsifiers are for example quaternary ammonium salts, for example quaternary ammonium salts or amine salts that contain at least one longchain alkyl or fluoroalkyl group, or a benzene or naphthalene group that is highly substituted with alkyl to yield the hydrophobic constituent.

Further suitable emulsifiers are the non-ionic surfactants in which .the hydrophilic constituent is a poly(ethoxy) group and the hydrophobic constituent is either a hydrocarbon or a fluorinated hydrocarbon group, e.g. the ethylene oxide condensates of alkylphenols, alkanols, alkylamines, alkylthiols, alkylcarboxylic acids, fluoroalkylcarboxylic acids, fluoroalkylamides and the like. Anionic emulsifiers are for example the sulphuric acid or phosphoric acid esters of the cited ethylene oxide condensates of long-chain alkylphenols, fatty alcohols, and fatty amines.

In the solvent polymerisation, the monomer(s) is are) dissolved in a suitable solvent, such as fluorinated solvents, for example hexafluoroxylene, benzotrifluoride, or mixtures thereof with acetone and/or ethyl acetate, and polymerised in a reaction vessel accompanied by the use of initiators such as azobisisobutyronitrile or other azo initiators, in concentration of 0.1 to 2%, at 40 to C under nitrogen.

Preferred solvents are hexafluoroxylene, benztrifluoride, fluorine substituted halogenated hydrocarbons, other fluorinated solvents and the like.

As stated at the outset, valuable copolymers with other ethylenically unsaturated monomers are obtained in the polymerisation of the new monomers in addition to homopolymers.

The carboxylic acid perfluoroalkyl esters according to the invention can be used as such or preferably as homoor copolymers for treating porous or non-porous substrates, preferably for producing oleophobic, hydrophobic, or dirt repellent finishes thereon. As porous substrates there may be mentioned leather and wood or especially fibre materials, such as textiles and paper. Possible non-porous substrates are chiefly metal, plastic, and glass surfaces.

The compounds according to the invention can also be used for example as additives for oils and lubricants for the prevention of wear and corrosion, or as additives for polishes and waxes.

Examples of textile materialsthat can be preferably treated with the monomeric or polymeric perfluoro compounds are those from natural or regenerated cellulose, such as cotton, linen, or rayon, staple fibre, or cellulose acetate. Also suitable are textiles made from wool, synthetic polyamides, polyester, or polyacrylonitrile. Blended fabrics or blended knitted fabrics from cotton/polyester fibres can also be finished with advantage. The textiles can be in the form of threads, fibres, flocks, fleeces, but preferably of woven or knitted fabrics, and can be'used for example as articles of clothing, upholstery materials, decorating materials, and carpets.

Preparations that contain the monomer or polymer perfluoro compounds can be applied to the substrate in known manner.

The substrates are provided withan oil-repellent finish by treating them both with solutions, such as dispersions oremulsions of the monomer or polymer perfluoro compounds. The monomers can be applied e.g. from a solution in an organic solvent to the textile material and, after evaporation of the solvent, fixed on the fabric by heat. Polymers can be also be applied to the fabrics from suitable solvents.

Fabrics can be impregnated e.g. by the exhaustion process or on a padder that is coated with the preparation at room temperature. The impregnated material is then dried at 60 to lC and subsequently optionally subjected to a heat treatment at over l00C, e.g. from 120 to 200C, advantageously in the presence of known catalysts that donate acid.

Examples of further application methods are spraying, brushing, roll-coating, dusting with subsequent heat fixing or transfer of the polymers from an auxiliary material (paper, foil) accompanied by the application of heat. Thecompounds according to the invention are applied in amounts of 0.1 to 10, preferably 0.5 to 5, percent by weight based on the substrate.

It is also possible to apply still further agents to the substrates simultaneously with the compounds according to the invention, e.g. wetting agents, soft-handle agents, water repellents, paraffin wax emulsions, resin finishes, or agents that impart crease resistance.

Besides the oil-repellent effect that is attained with the compounds according to the invention it is also possible in particular to achieve soil-release and antisoiling effects on textile fibre substrates: monomers, and among the polymers especially the copolymers, in which the substituents R R or R represents an alkoxy radical (R'-O), are particularly suitable for attaining these effects.

The following examples described the invention in more detail but are in no way limitative thereof. The parts and percentages are by weight unless otherwise stated.

EXAMPLES A. Manufacture of the carboxylic acid perfluoroalkyl esters la. 4.97 g of l-perfluorooctyl-2-chloroethanol and 1.42 g of triethylamine are dissolved in 25 ml of dry benzene. While stirring, a solution of l.l8 g of acrylic chloride in 10 ml of dry benzene is added within l5 minutes. The reaction mixture is allowed to react for 2 hours with stirring and the resulting precipitate is then filtered off. The filtrate is extracted with dilute sulphuric acid and then with dilute sodium bicarbonate solution. The benzene phase is subsequently dried over sodium sulphate and then fractionated, to yield 4.65 g (84.2% of theory) of the compound of the formula F oF2)8CIIo-( i-oI-1=o1n g ncl Boiling point: 54C/0.00l Torr.

Analysis: calculated C found C Molecular weight calculated found loin b. The procedure as described in (la) is carried out, but using fumaric dichloride. The fumaric acid diester of the formula is obtained.

Melting point: C (recrystallized from chloroform). Analysis: calculated C 26.8 H 0.8 Cl found C 26.9 H 0.9 CI

2. 3l g of a l-perfluoroalkyl-2-chloroethanol homologue mixture (only the principal components are indicated) of the formula M 11o l"g)nLiI[-Clh()l wherein n is 6, 8, l0, mol7z 20.0, 50.2, 24.8, are reacted with 8.74 g of triethylamine and 7.25 g of acrylic chloride in accordance with (1). There are obtained 28.85 g (84.1% of theory) of a homologue mixture of the fQlfltlil 1 oF, ,,oH-0o-oH=o1n wherein n is 6, 8, 10,

g sg d C 7 H 7 part of 2 normalacetic' acid, is vigorously stirred at D W gg e C H 20C for 20 minutes in a nitrogen atmosphere. Upon molecular weight: calclalated 548 addition of 25 parts of water the mixture is heated to foun 557.

60c and treated with a solution of 0.025 part of potassium peroxide disulphate in 1.5 parts of water and a so- The cpmpound can b poalymensedldurmg long W lution of 0.007 part of sodium metabisulphite in 1.5 anii yllesldls colofurlesls elasfltomersl-k I 2 th th parts of water. Ten minutes later there is again added h l g 9 a uoroa oxye am a solution of 0.025 'part of potassium peroxide disulomo Ogue mixture 0 t 6 m a phate in 1.5parts of water and a solution of 0.007 part (105) MCFDHCEFOH 10 of sodium metabisulphite in 1.5parts of water. A finely disperse, film-forming emulsion is obtained, which after 3 hours has a resin content of 19%, corresponding i 3, 10, to a yield of about 100%. 101% 231 49], b. In analogous manner to (a) the homologue mixare reacted with 5.38 g of triethylamine and 4.46 g of ture accqrding to (4) is polymerised' acrylic chloride in accordancewith (3) to yield 18.0 g A mxture of 10 parts of water sod'um (868% of theory) of a homologue u of the lauryl sulphate, 5 parts ofthe ester according to (2),

mula 4.8 parts of acrylic decyl ester, 0.2 part of N- V methylolacrylic amide, and 5 parts of acetone, is stirred 10s 0 vigorously for 20 minutes at 20c in a nitrogen atmo- F(CF2) GH O g CH=CH2 sphere, Upon addition of 25 parts of water the mixture is heated to 60C and treated with a solution of 0.025 part of potassium peroxide disulphate in 1.5 parts of water and a solution of 0.007 part of sodium metabisulphite in 1.5 parts of water. After 10 minutes there is again added a solution of 0.025 part of potassium peroxide disulphate in 1.5 parts of water and a solution of 0.007 part of sodium metabisulphite in 1.5 parts of water. A finely disperse film-forming emulsion is ob- O tained, which after 3 hours has a resin content of 17%,

omoorr.

wherein 25 n is 6, 8, l0. mol% 24.3, 50.3, 21.8, Boiling interval:100C/0.001 Torr.

5. Proceeding in analogous manner to manufacturing instruction (3) the following acrylicesters are obtained from the following l-perfluoroalkyl-2-alkoxy-alkanols l 4 corresponding to a yield of about 100% and lperfluoroalkyl2'arQXy?lkanOlS g 8. A mixture of IO-parts of water, 0.25 part of N- (107) dodecyltrimethyl ammonium chloride, 5 parts of the I ll compound of the formula 103, 4.8 parts of methacrylic F oF2 ..oH-oo-oH=oH2 octyl ester. 0.2 part of N-methylolacrylic amide, 5 parts Q@;Q:1 of acetone, and 0.05 part of 2 normal acetic acid, is sti- R n Boiling point Yield 1 Analysis 21) n-C,H,, 8 63C/0.001 Torr 76 calc. C 34,6 H 2.6

. found 34,9 2.7 b) n-C,H,, 6+8+10 53-103C/0.002 Torr 1 c) -CH,CH,0CH s 72C/0.001 Torr 81,3 calc. c 32.5 H 2.2 M 592 found 32,9 2,2 615 d) CH.,CH2OCH3 6+8+10 l03-l43C/l1 Torr 83,1 e) CEH5 8 l01C/0.00l Torr 80,0 calc. C 37,4 H 1,8

found 37.8 1,8

Molecular Composition n 6 8v Molecular Composition n l 5 g. 4.97 g of l-perfluorooctyl-2-chloroethanol ar rred vigorously for 20 minutes at 20C. Upon addition reacted with 1.42 g of triethylamine and 1.36 g of of 25 parts of water the mixture is heated to 60C and methacrylic chloride in analogous manner to Example treated with a solution of 0.025 part of potassium per- I. There are obtained 3.7 g (65% of theory) of the oxide disulphate in 1.5 parts of water and a solution of methacrylic ester v I 7 55 0.007 part of sodium metabisulphitein 1.5 parts of wa- (108) 053 0.025 part of potassium peroxide disulphate in 1.5 F(CF2)Q-CHOCC=CHZ parts of water and a solution'of 0.007 part of sodium C3201 metabisulphite in 1.5 parts of water. A finely disperse,

Boiling point; woe/M02 mm Hg. I film-forming emulsion is obtained, which after 3 hours Analysis calculated c 29.7H 1.1 2.2 has a resin content of 18%, corresponding to a yield of found c H about 100%. The following emulsion copolymers are manufactured according to instruction 8.

B. Manufacture of the polymers A mufture of 10 parts of a part of No. Fluorine-contain- Comonomerl Comonomcr2 N-dodecyltrlmethylammomum chlorlde, 0.25 part of ing monomer of the N-octadecyltrimethylammonium chloride, 9.8 parts of formula the ester according to (2), 0.2 part of N- 9 03 ac,y|icacid 2 methylolacrylic amide, 5 parts Of acetone, and 0.05 ethylhexyl ester acrylic amide ter. After 10 minutes there. is added again a solution of l Continued No. Fluorine-contain- Comonomer l Comonomer 2 ing monomer of the formula I I03 methacrylic acid do.

' nonyl ester ll I03 acrylic acid do.

decyl ester I2 I03 methacrylic acid do.

dodecyl ester I3 I03 methacrylic acid do.

hexyl ester l4 l07d methacrylic acid do.

nonyl ester 15 I06 methacrylic acid do.

nonyl ester 16 I03 acrylic acid-ndo.

butyl ester 17 I06 acrylic acid do.

decyl ester I8 I03 acrylic acid do.

hexyl ester 19a. A mixture of 10 parts of water, 0.25 part of dodecyltrimethylammonium chloride, 0.25 part of N-octadecyltrimethylammonium chloride, 7 parts of the compound of the formula l07f, 2.8 parts of acrylic acid decyl ester, 0.2 part of N-methylolacrylic amide, parts of acetone, and 0.05 part of 2 normal acetic acid, is stirred vigorously for 20 minutes at 20C. Upon addition of 25 parts of water the mixture is heated to 60C and treated with a solution of 0.025 part of potassium peroxide disulphate in L5 parts of water and a solution of 0.007 part of sodium metabisulphite in 1.5 parts of water. After minutes there is added again a solution of 0.025 part of potassium peroxide disulphate in l.5 parts of water and a solution of 0.007 part of sodium metabisulphite in 1.5 parts of water. A finely disperse, film-forming emulsion is obtained, which after 3 hours has a resin content of l8%, corresponding to a yield of about 100%.

b. In analogous manner to (a), the compound of the formula l07b is polymerised instead of the compound of the formula 107f.

a. A mixture of parts of water, 0.5 part of N-dodecyltrimethylammonium chloride, 0.3 part of N-octadecyltrimethylammonium chloride, 10 parts of the compound of the formula I06, and 5 parts of acetone, is heated to 60C and treated with a solution of 0.025 part of potassium peroxide disulphate in 1.5 parts of water and a solution of 0.007 part of sodium metabisulphite'in 1.5 parts of water. After minutes there is again added a solution of 0.025 part of potassium peroxide disulphate in 1.5 parts of water and a solution of 0.007 part of sodium metabisulphite in 1.5 parts of water. A finely disperse, film-forming emulsion is obtained, which after 3 hours has a resin content 0 19%, corresponding to a yield of 96%.

b. In analogous manner to (a), the compound of the formula 107a is polymerised instead of the compound of the formula I06.

C. Application of the Polymers I I. Cotton fabrics and polyester/cotton fabrics (65/35) are impregnated with the polymer emulsions. The amount of polymer applied is 2% and 4% respectively, based on the weight of the substrate. The impregnating preparations contain additionally one part of magnesium chloride hexahydrate per litre.

The impregnated fabric is dried in the air and heat fixed for 4 /2 minutes at I50C.

The finished fabrics are tested for their oil repellency according to the AATCC test procedure I I8-I966T of the American Association of Textile Chemists and colorists (AATCC). The repellencies are between 0 and 8, with 8 being the best value. The resistance ofthe finishing is also tested by washing the fabrics at 60C with an ordinary domestic detergent. The soilrelease properties are tested in the AATCC test procedure l30-l970 (Nujol Test). wherein nujol is applied at 40C before each domestic wash.

Application liquor of the polymers:

20-l40 parts of 15% emulsion of the polymers.

l part of magnesium chloride hexahydrate 979-859 parts of water.

The oil-repellency and soil-release values obtained are given in the following table.

Table l Polymer Amount of poly- Oil repellency on cotton according to mer in percent fabrics instruction by weight (based without after I after 5 on the fibre mawashing wash washes terial) 6a 4 5 34 3 6b 2 3 3 2 4 5 5 5 7 4 5 5 5 8 4 7 6 6 9 4 6 6 6 I0 2 2 2 I ll 2 6 6 6 I2 2 2 2 1 l3 2 4 4 4 I4 2 3 3 3 I5 2 5 5 5 l6 2 -l 4 3 l7 2 5 5 5 Table 2 polymer Amount of Oil repellency on cotton fabrics according to polymer in instruction percent by weight (based without after I after 5 on the fibre washing wash washes material) Table 3 Polymer Amount of Soil-release on cotton fabrics according to polymer in instruction percent by weight (based after I wash after 2 washes on the fibre material) 2. Fluorine-containing polymerisation products are applied with the following liquor:

20-l40 parts of 15% emulsion of the polymers 50 parts of an aqueous preparation (50%) consisting of l mole of hexamethylolmelamine-hexamethyl ether and 1 mole ofdimethylolethylene urea 8 parts of magnesium chloride hexahydrate 922-802 parts of water 1,000 parts Table 4 contains the results obtained of the oil repel- 5 lonic acid, n is a whole number from 4 to 14, and s is a whole number from 1 to 3.

4. Carboxylic acid perfluoroalkyl esters according to lcncy test: claim 3, which correspond to the formula Table 4 Polymer Amount of poly- Cotton Polyester/cotton according mer in percent bric to inslruby weight (based no after after no after after ction on fibre mater wash I wash 5 wushcs wash I wash 5 washes ial) 6a 4 5 4 4 5 4 4 6b 2 4 4 4 4 4 4 4 5 5 5 5 5 5 7 4 5 4 4 4 4 4 a 2 6 5-6 5-6 4 4-5 4 4 7 6-7 6 6 6 6 9 2 5 4-5 4 4 4 4 4 6 6 6 6 6 6 l 4 4 3 3 2 2 2 1 2 7 -6 5 3-4 3 2 4 7 6 6 6 6 5 l2 4 3-4 3 3 2-3 2-3 2-3 [3 2 5 4 3-4 3-4 3 2-3 We claim: (H) ll. Carboxylic acid perfluoroalkyl esters correspondmg to the formula V "l R CI-I A wherein R represents hydrogen or methyl, R repre- R J sents chlorine or the radical R '-O-, in which R repret &... ,t twig sents alkyl with 1 to 6 carbon atoms, cyclohexyl, P

wherein R, represents a perfluorinated hydrocarbon radical with l to 22 carbon atoms, R represents hydrogen or methyl, R, represents chlorine or the radical R,- O-, in which R, represents alkyl with l to 12 carbon atoms, cycloalkyl with 5 or 6 ring carbon atoms, alkoxyalkyl with 2 to 10 carbon atoms, the radical (CH CH O),,-R, in which R represents alkyl 1 to 6 carbon atoms and n is l or 2, or represents a phenyl radical or an alkylsubstituted phenyl radical with 1-4 carbon atoms'in the alkyl chain, A represents a hydrocarbon radical with 2 or 3 carbon atoms that is derived from monobasic, dibasic, or tribasic ethylenically unsaturated Carboxylic acids, and s is a whole number from 1 to 3.

2. Carboxylic acid perfluoroalkyl esters according to claim 1, wherein the perfluorinated hydrocarbon radical is a straight-chain or branched perfluoroalkyl radical with 4 to 17 carbon atoms.

3. Carboxylic acid perfluoroalkyl esters according to claim 1, which correspond to the formula or alkoxyalkyl with l to 3 carbon atoms in the alkoxy moiety, A represents an ethylenically unsaturated hydrocarbon radical that is derived from acrylic, methacrylic, crotonic, vinylacetic, fumaric, maleic, citranyl, or methoxyethyl, n is a whole number from 6 to 12, and A and s have the meanings given in claim 3.

5. Carboxylic acid perfluoroalkyl esters according to claim 4, which correspond to the formula wherein R A )1, and s have the meanings given in claim 4.

6. Carboxylic acid perfluoroalkyl esters according to claim 3, which correspond to the formula wherein R and R represent hydrogen or methyl, and R and n have the meanings given in claim 3.

7. Carboxylic acid perfluoroalkyl esters according to claim 6, which correspond to the formula wherein R and R represent hydrogen or methyl, and R and n, have the meanings given in claim 4.

* l l= l 

1. CARBOXYLIC ACID PERFLUOROALKYL ESTERS CORRESPONDING TO THE FORMULA
 2. Carboxylic acid perfluoroalkyl esters according to claim 1, wherein the perfluorinated hydrocarbon radical is a straight-chain or branched perfluoroalkyl radical with 4 to 17 carbon atoms.
 3. Carboxylic acid perfluoroalkyl esters according to claim 1, which correspond to the formula
 4. Carboxylic acid perfluoroalkyl esters according to claim 3, which correspond to the formula
 5. Carboxylic acid perfluoroalkyl esters according to claim 4, which correspond to the formula
 6. Carboxylic acid perfluoroalkyl esters according to claim 3, which correspond to the formula
 7. Carboxylic acid perfluoroalkyl esters according to claim 6, which correspond to the formula 